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CN1036525C - Block polyether-amide and its synthesis method - Google Patents

Block polyether-amide and its synthesis method Download PDF

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Publication number
CN1036525C
CN1036525C CN92100711A CN92100711A CN1036525C CN 1036525 C CN1036525 C CN 1036525C CN 92100711 A CN92100711 A CN 92100711A CN 92100711 A CN92100711 A CN 92100711A CN 1036525 C CN1036525 C CN 1036525C
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diacid
block
polyether
oligoamide
chain
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CN1063876A (en
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P·马
D·屈赞
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Arkema France SA
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Elf Atochem SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40—Polyamides containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
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    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
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    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
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Abstract

Block copolyetheramides, have the formula: in which D is the residue of a diacid oligamide having an &upbar& Mn ranging from 300 to 3,000 and/or the residue of the diacid chain limiter, PE is the residue of a polyetherdiol having an &upbar& Mn ranging from 200 to 5,000, these are prepared by polycondensing a multiblock polymer having the formula: with a diamine H2N-X-NH2.

Description

Block polyether-amides and synthetic method thereof
The present invention relates to contain the block polymer of polyether block and widowed phosphinylidyne amine block, this polymkeric substance also is called block polyether-amides.
Visible in the literature some bibliographys about block polyether-amides.
With the French Patent 2,273,021 and 2,401 that the applicant's name obtains, 947 have introduced the following formula polyether-amide:
Figure C9210071100041
Wherein A represents polyamide-block, and B represents the aliphatic polyether block.
Its preparation method is, under 100-400 ℃ and high vacuum, at one or more formulas M (OR) 4Metal four alkane oxide catalyzer (M represents titanium, hafnium or zirconium in the formula, and R represents C 1-C 24Alkyl) exist down, making Mn is 300-15, and 000 dicarboxylic acid polymeric amide and Mn are that the polyether glycol of 200-6000 reacts with molten state.
These block polyetheramides have favorable mechanical and chemical property.
French Patent 2,384,810 have introduced polyether-ester-amide, its preparation method is in the presence of 230-300 ℃ and autogenous pressure and water, making by one or more monomer of polyamide, a kind of Mn is the α of 160-3000, the mixture that alpha, omega-dihydroxy (polytetrahydrofuran) or PTMG and at least a diacid constitute carries out polymerization, dewaters from reaction mixture then, polymerizing condition is returned to u250-280 ℃ and normal pressure or decompression again.
The product that obtains also is sequence or block polymer, and has good low temperature impact strength.
But the polymkeric substance that obtains according to these patents has the fusing point lower than polymkeric substance of the present invention for given hardness.
United States Patent (USP) 4,307,227 have introduced Hotmelt Adhesive, and this class tackiness agent is made of the repeating unit that is obtained from hexanolactam of 50-80% and the mixture of dicarboxylic acid, primary amine and polyoxyalkylene glycol.
Used method (making all components reaction under 220 ℃ of-250 ℃ of catalyst-frees) can not synthesize wherein, and the Mn of polyether block is higher than 1000 product.
J63-035622 and J63-277239 patent application relate to block polyether-amides, its preparation method is to be higher than under 250 ℃ the temperature and high vacuum, in the presence of the esterifying catalyst of metal four alkane oxide, make the PA-6 that contains one or more polyoxy alkylidene dioxy blocks, 6 widowed phosphinylidyne amines and lower molecular weight polyether polyols or a kind of glycol react.
With the product that lower molecular weight polyether polyols or glycol obtain, its fusing point is starkly lower than the fusing point of product of the present invention.
The J63-182343 patent application relates to block polyether-amides, and its preparation method is to make the PA-6 that has two amine end groups, and 6 segments carry out the molten state reaction with the polyethers that has dicarboxylic acid end chain.The polymkeric substance that obtains according to the method for this application has the high-melting-point more than 230 ℃, but therefore demanding invert point has the danger of product degradation in its conversion process.
Block polyether-amides of the present invention is a thermoplastic elastomer, and wherein the most possible chain of each block can be represented by following general formula:
Wherein:
It is diacid widowed phosphinylidyne amine residue and/or diacid chain-limiting agent (Limiter) residue of 300-3000, preferred 500-2000 that D represents Mn,
It is the polyether diol residue of 200-5000, preferred 200-3000 that PE represents Mn,
X represents C 4-C 20, preferred C 6-C 15Straight chain or branching (ring) aliphatic series or aromatic hydrocarbons chain,
N is 1-4, preferably near 1, and
M is average 2-50, preferred 5-20.
Be appreciated that block polyether-amides of the present invention can be made of D of different nature and PE block.That can mention as an example, has widowed phosphinylidyne amine block wherein by one side PA-6 oligomer, the block polyether-amides that constitutes of PA-12 oligomer on the other hand.
Used diacid widowed phosphinylidyne amine can by polymerization lactan and/or amino acid in the presence of a kind of diacid chain-limiting agent and arbitrarily one or more following diacid of 50% (weight) of adding of choosing obtain with one or more diamines and/or its salt.
Preferred widowed phosphinylidyne amine is those widowed phosphinylidyne amines that obtained by hexanolactam and/or laurolactam.
In the diacid chain-limiting agent, that mentions especially has hexanodioic acid and terephthalic acid, a preferred dodecandioic acid.
The example of the polyether glycol that can mention is as follows: polyoxyethylene glycol (PEG), polypropylene glycol (PPG) and polytetramethylene glycol (PTMG), and the mixture of at least two kinds of above-mentioned polyether glycols, preferred especially PEG of the applicant and PTMG itself.
As the example of copolyether glycol, the statistics that ethylene glycol and/or propylene glycol and/or butyleneglycol are arranged that can mention/or segmented copolymer.
The logarithmic viscosity number of block polyether-amides of the present invention is generally 0.6-2.5dl/g, preferred 0.8-2, preferably 1-1.8.Its condition determination be 20 ℃ in meta-cresol, the initial concentration of polymkeric substance be 0.5 the gram/100 the gram meta-cresols.
Its number-average molecular weight is generally 10,000-50, and 000, preferred 15,000-30,000.
Block polyether-amides of the present invention can prepare in two steps.
Many blocks of following formula diacid product
Figure C9210071100061
Can produce by polycondensation diacid widowed phosphinylidyne amine and polyether glycol, also can be by the widowed phosphinylidyne amine monomer, diacid chain-limiting agent and polyether glycol preparation.Can be according to synthetic these the many blocks products of any known polycondensation method, for example solution or interface polycondensation, and preferred molten polycondensation.For every mole of polyether glycol, general diacid widowed phosphinylidyne amine or diacid widowed phosphinylidyne amine chain-limiting agent with (n+1) mole, wherein the n definition is as above.
Carry out melt polycondensation reaction and generally be under 230-280 ℃ and normal atmosphere or under initial water vapor pressure, and then under normal atmosphere.
Then, make above-mentioned many blocks product and formula NH 2-X-NH 2Diamines carry out molten state and react to synthesize block polyether-amides of the present invention.
In preferred diamines, that can mention has m-xylene diamine, two (4-aminocyclohexyl) methane, 1, a 6-hexanediamine, particularly ten dimethylene diamines.Every mole of diacid widowed phosphinylidyne amine uses 0.8-1.3 mole diamines more favourable, preferred 0.9-1.15 mole.
Above-mentioned two steps can be used esterification and amidation catalyst respectively, can and/or add these catalyzer in building-up process in the reaction beginning.
The example of esterifying catalyst can be mentioned a zinc acetate, and the example of amidation catalyst can be mentioned phosphorous acid H 3PO 2
These steps can under reduced pressure be carried out.
Block polyether-amides of the present invention can use separately, and is applicable to production molding and extruded product, film, sheath and matrix material, as multilayer film; Also can mix use with other polymkeric substance, particularly polymeric amide.
Block polyether-amides more of the present invention have special property.
As an example, can mention such block polyether-amides, wherein polyether block mainly form by PEG and itself or as having excellent static resistance and ventilation property with other mixture of polymers, other polymkeric substance has for example ABS resin, polycarbonate, polyphenylene ether or polymeric amide.
In anlistatig block polyetheramides, preferably wherein the widowed phosphinylidyne amine block is the block polyether-amides that is obtained by PA-6.In gas-pervious block polyether-amides, preferably its widowed phosphinylidyne amine block is the block polyether-amides that is obtained by PA-12.
Following examples have illustrated the present invention, rather than in order to limit the present invention.
In text in the whole text, Mn is a number-average molecular weight.Shore D (5S) is measured according to iso standard R868.
Synthesizing of three block products
Embodiment 1
In 4 liters of stainless steel autoclaves being furnished with anchor stirrer, to add 350 gram Mn and be 2000 PTMG two pure and mild 360 gram Mn be 1028, be 148 ℃ the few acid amide of PA-12 diacid by adipic acid limit chain and fusing point.
After 5 crust nitrogen purge 4 times, reactor content is placed under the mitigation nitrogen gas stream under the normal atmosphere, and be heated to 260 ℃, last 100 minutes.Reacted under these conditions 120 minutes, the product that obtains contains 0.49 milligramequivalent/restrain remaining acid functional group, and the Mn that is equivalent to product is 4080, fusing point is 153 ℃.
Embodiment 2
Under the similarity condition of embodiment 1, under 260 ℃ and nitrogen gas stream, making 604 gram Mn is that 2000 PTMG two pure and mild 613 gram Mn are 1015, are that 147 ℃ PA-12 diacid widowed phosphinylidyne amine reacts by dodecanedioic acid limit chain and fusing point.Be heated to after 260 ℃ with 100 minutes, the Mn that obtain containing 0.49 milligramequivalent/restrain remaining acid functional group after 65 minutes in this thermotonus, is equivalent to product be 4080 and fusing point be 155 ℃ three block products.
Embodiment 3
At embodiment 1 similarity condition, making 350 gram Mn is that 2000 PTMG, two pure and mild 327 gram Mn are 933, are that 155 ℃ PA-12 diacid widowed phosphinylidyne amine reacts by terephthalic acid limit chain and fusing point.Be heated to 260 ℃ and under this temperature and nitrogen gas stream, after the reaction 150 minutes, obtain containing the product of 0.54 milligramequivalent/remaining acid functional group of gram with 50 minutes, the Mn that is equivalent to product be 3700 and fusing point be 147 ℃.
Embodiment 4
Under embodiment 1 similarity condition, make 200 gram Mn be 2000 PTMG, two pure and mild 400 gram Mn be 2000 and fusing point be that 160 ℃ PA-12 diacid widowed phosphinylidyne amine reacts.Be heated to 260 ℃ and after the reaction 300 minutes, obtain three block products under this temperature with 45 minutes, it contains the acid functional group of 0.335 milligramequivalent/gram remnants, and the Mn that is equivalent to product is that 5970 (target Mn is 6000) and fusing point are 169 ℃.
Synthesizing of block polyether-amides of the present invention
Embodiment 5
A useful volume is 100cm 3, be furnished with in the glass reactor of glass anchor stirrer, nitrogen inlet pipe and condenser, add diacid three block products that 30 gram embodiment 1 obtain and ten dimethylene diamines of 1.53 grams, be equivalent to 1.04 moles of diamines of every mole of diacid three block products.
After reactor is with nitrogen purge, it is immersed in 220 ℃ of oil baths.Begin to stir after the reaction mixture fusing, temperature is raised to 260 ℃ in 40 minutes.Sustained reaction is 3 hours under this temperature, then reaction mixture is placed under the vacuum gradually, until obtaining about 13.3Pa residual pressure.After 2 hours, reaction mixture is returned to normal atmosphere gradually under these conditions, stop then stirring, and from thermostatic bath, take out reactor to stop heating by nitrogen injection.After the cooling, obtain thermoplastic elastomer, its logarithmic viscosity number is 0.84dl/g, 153 ℃ of fusing points.
Embodiment 6
The condition that adopts embodiment 5 to introduce, diacid three block products and 1.55 grams, ten dimethylene diamine reactants that 30 gram embodiment 2 are obtained.
Under the normal atmosphere nitrogen gas stream, 30 minutes, 260 ℃ reactions of 15 minutes, 240 ℃ reactions of 220 ℃ of reactions 50 minutes obtain thermoplastic elastomer in reaction under the decompression of about 26.6Pa after 3 hours 30 minutes at last, its fusing point is 158 ℃, and logarithmic viscosity number is 0.78dl/g.
Embodiment 7
The condition that adopts embodiment 5 to introduce makes the three block products and 1 of 20 gram embodiment 3 restrain ten dimethylene diamine reactants.Reactor is placed about 133Pa decompression down, made temperature be raised to 200 ℃ with 5 minutes then.Begin to stir, and make reaction mixture (still being in decompression down) in 15 minutes, be raised to 260 ℃, make pressure drop to about 13.3Pa.
After reacting 60 minutes under these conditions, collect thermoplastic elastomer, its fusing point is 163 ℃, and logarithmic viscosity number is 0.6dl/g.
Embodiment 8
The condition that adopts embodiment 5 to introduce, triblock polymer, 1.5 gram ten dimethylene diamines and 6 μ l50% Hypophosporous Acid, 50 reactant aqueous solutions that 30 gram embodiment 1 are obtained.The reaction mixture that will be under the nitrogen gas stream with 5 minutes times is raised to 220 ℃, under this temperature the insulation 10 minutes, in 7 minutes, be raised to then 240 ℃ and under this temperature the insulation 63 minutes.
At last, reaction mixture is raised to 260 ℃, and under this temperature, is incubated 3 hours with 7 minutes.Obtain thermoplastic elastomer thus, its logarithmic viscosity number is 1dl/g, 156 ℃ of fusing points.
Embodiment 9
Press embodiment 5 similar fashion, the three block products that 30 gram embodiment 1 are obtained, 1.5 gram ten dimethylene diamines and 0.06ml 50% Hypophosporous Acid, 50 reactant aqueous solutions.After 260 ℃ of reactions under atmospheric pressure purged with nitrogen in 105 minutes simultaneously, obtain thermoplastic elastomer, its logarithmic viscosity number is 1.15dl/g, 154 ℃ of fusing points.
Embodiment 10
Press embodiment 9 similar fashion, the three block products, 1.73 that 34.2 gram embodiment 1 are obtained restrain the Hypophosporous Acid, 50 reactant aqueous solution of ten dimethylene diamines and 0.6ml 50%.
With 3 minutes time, reaction mixture is heated to 240 ℃ under the normal atmosphere nitrogen gas stream, and under this temperature, is incubated 10 minutes, in 8 minutes, be raised to 260 ℃ then.After this temperature 38 minutes, obtain thermoplastic elastomer, its logarithmic viscosity number is 1.08dl/g, 146 ℃ of fusing points.
Embodiment 11 (comparative example)
The method of introducing according to the J63-035621 patent application, three block products that 30 gram embodiment 1 are obtained and 7.1 gram Mn are that 1000 PTMG places 100cm similar to Example 5 3In the glass reactor.Reactor immerses in the oil bath that remains on 260 ℃ with after the nitrogen purge.After the reaction mixture fusion, begin to stir.After under the nitrogen gas stream normal atmosphere, reacting 2 hours, pressure is dropped to 13.3Pa with 30 minutes.Add 0.1 gram Zr (OBu) after 10 minutes 4, produce kickback.Stop after 20 minutes stirring, utilize nitrogen circulation that reaction mixture is returned under the normal atmosphere, from oil bath, take out pipe then, allow it at room temperature cool off.The fusing point of the thermoplastic elastomer that obtains is 142 ℃, and logarithmic viscosity number is 1.53dl/g.
Embodiment 12 (comparative example)
Press embodiment 11 similar fashion, 260 ℃ of three block products and 0.85 gram decamethylene-glycol reactions that 20 gram embodiment 1 are obtained.Under this temperature, after following 1 hour of nitrogen gas stream normal atmosphere, in 40 minutes, pressure is dropped to 13.3Pa.After this thermotonus 100 minutes, add 0.3 gram Zr (OBu) 4, and mixture kept 90 minutes under this pressure.The logarithmic viscosity number of the thermoplastic elastomer that obtains is 1.14dl/g, 149 ℃ of fusing points.
Embodiment 13
Be furnished with the turbine agitator and use in advance in 880 liters of stainless steel autoclaves of nitrogen purge at one, make 95kg lauryl hexanolactam and 28.4kg dodecandioic acid in the reaction 2 hours down of 290 ℃ of autogenous pressures.Return to after the normal atmosphere, introducing 123.6kg Mn is 2000 PTMG, and mixture was reacted 3 hours down in 240 ℃ of nitrogen gas stream normal atmosphere.With 7.2kg 1, the 6-hexanediamine after the homogenizing 1 hour, makes reaction mixture return to normal atmosphere, and places 880 liters of stainless steel reactors being furnished with the anchor agitator under 240 ℃ of autogenous pressures.Introduce after the phosphate aqueous solution of 240 grams 84%, mixture is placed 5.3 * 10 3Under the decompression of Pa, polycondensation obtained thermoplastic elastomer after 6 hours under these conditions, and its fusing point is 150 ℃, logarithmic viscosity number 1.12dl/g, and Shore D is 28.9.
Embodiment 14 (comparative example)
By the method that French Patent 2384810 is introduced, pack in being furnished with 100 liters of stainless steel autoclaves of anchor agitator 11.545kg lauryl hexanolactam, 3.454kg dodecandioic acid, 0.87kg1,6-hexanediamine, 15kgMn are 2000 PTMG and 2 premium on currency.After several times of nitrogen purge, under 25 crust water vapor pressures, stirring whole article are being heated to 270 ℃, kept this condition simultaneously 8 hours.
Be pressed onto normal atmosphere and with after the nitrogen purging with unloading in 90 minutes, introduce 36.8g 84% phosphate aqueous solution and lasting polycondensation 9 hours under 270 ℃ of nitrogen gas stream normal atmosphere.Obtain thermoplastic elastomer, its logarithmic viscosity number is 1.58dl/g, and fusing point is 147 ℃, and Shore D is 34.6.
Embodiment 15 (comparative example)
According to the method for introducing in the French Patent 2401947, pack in 100 liters of stainless steel autoclaves being furnished with the anchor agitator 11.544kg lauryl hexanolactam, 3.454kg dodecandioic acid, 0.87kg1,6-hexanediamine and 2.9 premium on currency.Wash down after several times with nitrogen, mixture is heated to 270 ℃ under 32 crust autogenous pressures, and kept these conditions 3 hours.
With the pressure normal atmosphere that reduces pressure, the mixture nitrogen purging is introduced 15kg Mn and is 2000 PTMG then.Stirred 3 hours remaining on 250 ℃ of mixtures under the nitrogen gas stream, then pressure is reduced pressure 50 millibars gradually, and reduce the temperature to 240 ℃.Then, introduce 60cm 3Zr (OBu) 480% solution in butanols.After 10 minutes, pressure is reduced to 10 millibars.After 15 minutes, obtain the white hot thermoplastic elastic under these conditions, its logarithmic viscosity number is 1.08dl/g, 145 ℃ of fusing points, and Shore D is 34.3.
Embodiment 16
According to the similar fashion of embodiment 13, after several times of nitrogen purge reactor, 126kg lauryl hexanolactam and 37.8kg dodecandioic acid were reacted 2 hours down in 290 ℃ of autogenous pressures.Return to after the normal atmosphere, introducing 82kg Mn is 1000 PTMG, and mixture was reacted 3 hours under 240 ℃ of nitrogen gas stream normal atmosphere.
Under 240 ℃ of autogenous pressures, with 9.54kg 1, after the 6-hexanediamine homogenizing 1 hour, reaction mixture is transferred in the stainless steel reactor of being furnished with the anchor agitator, and unloaded with 1 hour and to be pressed onto normal atmosphere.The phosphate aqueous solution of 240g 84% is added in the reaction mixture, places 4 * 10 gradually 3Under the condition of Pa decompression.After the polymerization 4 hours, obtain thermoplastic elastomer under these conditions, its fusing point is 148 ℃, logarithmic viscosity number 1.26dl/g, and Shore D is 42.7.
Embodiment 17 (comparative example)
Press the similar fashion of embodiment 14, in 1001 stainless steel autoclaves of being furnished with the anchor agitator, add 15.394kg lauryl hexanolactam, 4.606kg dodecandioic acid, 1.162kg 1,6-hexanediamine, 10kg Mn are 1000 PTMG and 1 premium on currency.After several times of nitrogen purge, under stirring and 15 crust water vapor pressures, whole article are heated to 270 ℃, and kept under these conditions 8 hours.Be pressed onto normal atmosphere and, introduce the phosphate aqueous solution of 37.1 grams 84% with unloading in 25 minutes, and make polycondensation continue 4 hours down in 270 ℃ of nitrogen gas stream normal atmosphere with after the nitrogen purging.The logarithmic viscosity number of the thermoplastic elastomer that obtains is 1.58dl/g, and fusing point is 146 ℃, and Shore D is 47.3.

Claims (11)

1.两步合成下式嵌段聚醚-酰胺的方法：
Figure C9210071100021
1. the method for two-step synthesis following formula block polyether-amide:
Figure C9210071100021
 其中D代表Mn为300-3000的二酸寡酰胺残基和/或二酸限链剂残基，PE代表Mn为200-5000的聚醚二醇残基，X代表C4-C20的直链或支化(环)脂族或芳烃链，n为1-4的整数以及m平均为2-50，Wherein D represents diacid oligoamide residue and/or diacid chain limiter residue with Mn of 300-3000, PE represents polyether diol residue with Mn of 200-5000, X represents C 4 -C 20 straight chain or branched (cyclo)aliphatic or aromatic chain, n is an integer from 1 to 4 and m is on average 2 to 50, 该方法的步骤包括：The steps of the method include: a)通过界面或溶液缩聚法将二酸寡酰胺和聚醚二醇或寡酰胺单体、二酸限链剂和聚醚二醇缩聚来制备下式的多嵌段产物：
Figure C9210071100022
以及a) polycondensation of diacid oligoamide and polyether diol or oligoamide monomer, diacid chain-limiting agent and polyether diol by interfacial or solution polycondensation method to prepare the multi-block product of the following formula:
Figure C9210071100022
as well as b)使a)得到的多嵌段产物以熔融态与式NH2-X-NH2的二胺反应。b) reacting the multi-block product obtained in a) in molten state with a diamine of the formula NH2- X - NH2 . 2.按照权利要求1所述的方法，其特征在于嵌段聚醚-酰胺式中D代表Mn为500-2000的二酸寡酰胺残基，                     PE代表Mn为200-3000的聚醚二醇残基，X代表C6-C15的直链或支化(环)脂族或芳族链，n为1以及m平均为5-20。2. according to the described method of claim 1, it is characterized in that D representative Mn is the diacid oligoamide residue of 500-2000 in the block polyether-amide formula, and PE represents the polyether diol residue that Mn is 200-3000 group, X represents a C 6 -C 15 linear or branched (cyclo) aliphatic or aromatic chain, n is 1 and m is 5-20 on average. 3.按照权利要求1的方法，其特征在于二酸寡酰胺是通过在二酸限链剂或其盐存在下聚合内酰胺和/或氨基酸和任意选加的50％(重量)以下的一种或多种二酸以及一种或多种二胺得到的。3. according to the method for claim 1, it is characterized in that diacid oligoamide is by in the presence of diacid chain-limiting agent or its salt, polylactam and/or amino acid and arbitrarily selected 50% (weight) below a kind of or more diacids and one or more diamines. 4.按照权利要求1的方法，其特征在于聚醚二醇选自PEG和/或PPG和/或PTMG和/或乙二醇和/或丙二醇和/或丁二醇的无规和/或嵌段共聚物。4. according to the method for claim 1, it is characterized in that polyether diol is selected from random and/or block of PEG and/or PPG and/or PTMG and/or ethylene glycol and/or propylene glycol and/or butanediol copolymer. 5.按照权利要求1-4中任一项的方法，其特征在于所得嵌段聚醚-酰胺的比浓对数粘度为0.6-2.5dl/g。5. Process according to any one of claims 1-4, characterized in that the resulting block polyether-amide has an inherent viscosity of 0.6-2.5 dl/g. 6.按照权利要求3的方法，其特征在于二酸寡酰胺是由己内酰胺和/或十二内酰胺得到的。6. Process according to claim 3, characterized in that the diacid oligoamide is obtained from caprolactam and/or laurolactam. 7.按照权利要求5的方法，其特征在于所述比浓对数粘度为0.8-2dl/g。7. Process according to claim 5, characterized in that said inherent viscosity is 0.8-2 dl/g. 8.按照权利要求7的方法，其特征在于所述比浓对数粘度为1-1.8dl/g。8. Process according to claim 7, characterized in that said inherent viscosity is 1-1.8 dl/g. 9.按照权利要求1的方法，其特征在于步骤a)中采用熔融态缩聚法制备多嵌段产物。9. The method according to claim 1, characterized in that in step a), the multi-block product is prepared by polycondensation in a molten state. 10.按照权利要求1的方法，其特征在于步骤b)中所述二胺为间二甲苯二胺，双(4-氨基环己基)甲烷，1，6-己二胺和/或十二亚甲基二胺。10. according to the method for claim 1, it is characterized in that the diamine described in step b) is m-xylylene diamine, two (4-aminocyclohexyl) methane, 1,6-hexamethylene diamine and/or dodecylene Methyldiamine. 11.按照权利要求1的方法，其特征在于其步骤的一步和/或另一步中使用催化剂。11. Process according to claim 1, characterized in that a catalyst is used in one and/or the other of the steps.
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